Systems and methods for enhanced inorganic contaminant removal from hydrocarbon feedstock

ABSTRACT

Systems and methods to enhance the removal of inorganic contaminants, including metals, from hydrocarbon feedstocks at a refinery. One or more embodiments of such systems and methods may be used to provide a renewable hydrocarbon feedstock having a reduced amount of metal contaminants. The reduction of metal contaminants in the renewable hydrocarbon feedstock mitigates catalyst fouling and/or deactivation during downstream refinery processing of the renewable hydrocarbon feedstock.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. Non-Provisional applicationSer. No. 17/452,678, filed Oct. 28, 2021, titled “SYSTEMS AND METHODSFOR ENHANCED INORGANIC CONTAMINANT REMOVAL FROM HYDROCARBON FEEDSTOCK,”which claims priority to and the benefit of U.S. Provisional ApplicationNo. 63/198,606, filed Oct. 29, 2020, titled “REFINERY SYSTEMS ANDMETHODS FOR SEPARATING WATER FROM PRE-TREATED FEEDSTOCK,” U.S.Provisional Application No. 63/198,937, filed Nov. 24, 2020, titled“REFINERY SYSTEMS AND METHODS FOR SEPARATING WATER AND REMOVING SOLIDSFROM PRE-TREATED AND UNFILTERED FEEDSTOCK,” and U.S. ProvisionalApplication No. 63/198,960, filed Nov. 25, 2020, titled “SYSTEMS ANDMETHODS FOR ENHANCED INORGANIC CONTAMINANT REMOVAL FROM HYDROCARBONFEEDSTOCK,” the disclosures of which are incorporated herein byreference in their entirety.

FIELD OF THE DISCLOSURE

The disclosure herein relates to refinery systems and methods forinorganic contaminant removal from hydrocarbon feedstocks. One or moreembodiments of such systems and methods may be suitable for enhancedinorganic contaminant removal from a renewable hydrocarbon feedstock atthe refinery.

BACKGROUND

Due to demand for renewable transportation fuel, various feedstock ofvarying levels of contamination may be considered. Such biomass-derivedor renewable feedstock may be relatively inexpensive, but due to thecontamination, may require pre-treating prior to processing in arefinery. Such feedstock may include plant oils, algal and microbialoils, waste vegetable oils, yellow and brown grease, tallow, soap stock,pyrolysis oils from plastic or cellulose, and petroleum fractions. Thefeedstock listed may not be usable due to contamination unless, asnoted, pre-treated prior to being utilized in typical refineryoperations. Such contamination may cause issues in refinery equipmentand operations.

For example, renewable plant oils typically contain phospholipidcompounds or complexes. The phosphorous in phospholipids may createissues in refinery equipment, as noted below. For example, phosphorusmay poison and deactivate catalysts utilized in hydrotreating,hydrocracking, and hydroisomerization processes. Metals are also presentin renewable feedstocks, and can include alkali metals (e.g., sodium,potassium, etc.), metalloids (boron, silicon, arsenic, etc.), and othermetals (e.g., calcium, iron, magnesium, nickel, etc.). Such metals arealso known to poison and deactivate catalysts utilized in hydrotreating,hydrocracking, hydroisomerization, and other catalytic refiningprocesses. Such issues presented by phosphorus and metal contaminantsmay lead to more frequent catalyst replacement, which may increaseoperation costs significantly. Catalysts may be protected using guardbeds containing alumina or similar high-surface area materials. Thealumina or similar material may absorb low concentrations of metal andphosphorus compounds. Such an approach may increase cost, however, forrenewable feedstock, as the renewable feedstock may contain high levelsof metals and phosphorus compounds. Further, phosphorus is a nucleatingsite and catalyst for coke formation. As such, renewable plant oils andother feedstock that are high in phosphorus may cause fouling or cokingin fired-furnaces and heat exchangers. These issues, namely fouling andcoking, may increase downtime, for example, for decoking andmaintenance.

There are several methods to remove metals and phosphorus compounds,including the hydrothermal cleaning process or hydrothermal reaction.Such a process may include combining a renewable feedstock or otherfeedstock having high levels of metals and/or phosphorus compounds withwater. The water and feedstock may be heated and transported to ahydrothermal reactor. Utilizing a combination of temperature (forexample, about 465° F. to about 575° F.), pressure, and flow conditionsover a period of time, the hydrothermal reactor may wash the metals orphosphorus compounds from the renewable feedstock into the watercontained in the water and feedstock mixture. Prior to furtherrefinement of the feedstock in a refinery, the water may be separatedfrom the feedstock.

Salt compounds may typically be limited in crude feedstock for similarreasons as metals and phosphorus, as noted above. For example, saltcompounds may cause corrosion, coking, and/or catalyst fouling issues.Conventional desalting processes (for example, via an electrostaticprecipitation unit and/or crude desalter unit) may mix petroleum crudeoil and water at elevated temperatures through a mixing valve to form amixed or blended stream. The mixed or blended stream may be fed to alarge oil-water separator. The water in the mix or blend may absorb thesalt compounds. The separation of water (e.g., the water including thesalt compounds) from the feedstock may be facilitated by passing highfrequency alternating current or a direct current (for example, via anelectrostatic precipitation unit including a grid-like structure ofelectrodes) through the mixture or blend of the water and feedstock tocause small water droplets to form. Demulsifying agents may also beutilized to facilitate removal of water. Typically, renewable feedstock,such as waste vegetable oil, yellow and brown grease, and tallow, werethought to be difficult to desalt using conventional electrostaticprecipitation units and/or crude desalter units, in part, due to theconductivity of these oils and their potential to form soaps andemulsions.

Typically, a large separator (for example, a Stokes Law separator) isused to remove water from pre-treated feedstock following a hydrothermalcleaning unit or hydrothermal reactor. In such examples, the largeseparator may not be typical for a refinery and may take up largeamounts of space, thus increasing overall refinery operation costs anddecreasing available real estate for other processes and/or equipment.Further, such a separator may not completely remove the water frompre-treated feedstock from the hydrothermal cleaning unit orhydrothermal reactor (e.g., such a separator may remove all but 2% ofwater from the pre-treated feedstock). While the amount of metal and/orphosphorus leftover may be small, over time such a small amount mayaccumulate in downstream refinery equipment, causing fouling and/orcoking, among other issues. Further still, the separator may take longerperiods (for example, hours rather than minutes) of time to remove thewater, since such a separator may rely on time for the feedstock andwater to naturally separate or settle.

Accordingly, Applicants have recognized a need for systems and methodsto enhance the separation of inorganic contaminants, including metals,from renewable hydrocarbon feedstocks at the refinery. The presentdisclosure is directed to embodiments of such systems and methods.

SUMMARY OF THE DISCLOSURE

The present disclosure is generally directed to systems and methods toreduce inorganic contaminants in renewable hydrocarbon feedstocks at arefinery. In one embodiment, the process includes passing water throughan ion exchange system to generate deionized water having a conductivityof less than about 3 μS/cm and mixing the deionized water with arenewable feedstock that contains hydrocarbon compounds and inorganiccontaminants to create a deionized water and renewable feedstockmixture. This mixture is reacted in a hydrothermal reactor at atemperature, pressure and non-laminar flow that does not causerearrangement reactions of the renewable feedstock hydrocarboncompounds. As such, the non-laminar flow has a Reynolds number greaterthan 2,000. The reaction in the hydrothermal reactor is maintained atthe temperature, pressure and non-laminar flow for a first time intervalin order to transfer at least a portion of the inorganic contaminants ofthe renewable feedstock into the deionized water. After the first timeinterval, the deionized water and renewable feedstock mixture is passedto a separation unit in which the deionized water containing theinorganic contaminants is separated from the renewable feedstock. Duringa second time interval, this separation creates a contaminant-rich waterand a reduced-contaminant renewable feedstock. After the second timeinterval, the reduced-contaminant renewable feedstock is passed to adownstream refinery process. In another embodiment, the water passed tothe ion exchange system is first passed through a reverse osmosis unitto remove solids. The water treated by reverse osmosis is then passed tothe ion exchange system and the process continues as described above.

In another embodiment, the process includes passing water through an ionexchange system to generate deionized water having a conductivity ofless than about 5 μS/cm. The deionized water is then aerated in anaerating unit to increase the concentration of dissolved oxygen in thedeionized water and thereby generate an aerated, deionized water. Theaerated, deionized water is injected into a renewable feedstock streamat a refinery to create a mixture of aerated, deionized water andrenewable feedstock. This mixture is reacted in a hydrothermal reactorat a temperature, pressure and non-laminar flow that does not causerearrangement reactions of the renewable feedstock hydrocarboncompounds. As such, the non-laminar flow has a Reynolds number greaterthan 2,000. The reaction in the hydrothermal reactor is maintained atthe temperature, pressure and non-laminar flow for a first interval oftime in order to transfer at least a portion of the inorganiccontaminants of the renewable feedstock into the aerated, deionizedwater. After the first time interval, the mixture is passed to aseparation unit of the refinery. During a second time interval, theaerated, deionized water containing the inorganic contaminants isseparated from the renewable feedstock to create contaminant-rich waterand a reduced-contaminant renewable feedstock. After the second timeinterval, the reduced-contaminant renewable feedstock is passed to adownstream processing unit of the refinery. In an alternativeembodiment, the water is aerated in the aeration unit prior to beingtreated in the ion exchange system. In another embodiment, the waterpassed to the ion exchange system is first passed through a reverseosmosis system to remove solids. The water treated by reverse osmosis isthen passed to the ion exchange system and the process continues asdescribed above. In this latter embodiment, the water may be aeratedprior to treatment by reverse osmosis, after treatment by reverseosmosis, or after treatment by the ion exchange system.

A refinery system for reducing contaminants in renewable hydrocarbonfeedstocks is disclosed. In one embodiment, the refinery system includesa source of a renewable feedstock having hydrocarbons compounds andinorganic contaminants and a source of water. The refinery system alsoincludes a deionized water generator in fluid communication with thesource of water, whether such water is non-deaerated or aerated. Thedeionized water generator is arranged and designed to generate a streamof deionized water having a conductivity of less than about 1 μS/cm. Amixer in fluid communication with the source of renewable feedstock andin fluid communication with the deionized water stream is provided, andthe mixer is configured to receive the deionized water stream andrenewable feedstock stream to thereby create a mixture of deionizedwater and renewable feedstock. The refinery system also includes ahydrothermal cleaning unit, positioned at the refinery, in fluidcommunication with the mixer to receive the mixture. The hydrothermalcleaning unit is configured to transfer inorganic contaminants containedin the renewable feedstock into the deionized water during a first timeinterval. An oil-water separator, at the refinery, is in fluidcommunication with the hydrothermal cleaning unit. The oil-waterseparator is configured to receive the mixture from the hydrothermalcleaning unit and provide a residence time to separate the renewablefeedstock from the deionized water containing the inorganiccontaminants, thereby generating a reduced-contaminant renewablefeedstock. In one or more embodiments, the refinery system also includesa downstream refinery process unit in fluid communication with theoil-water separator and configured to receive the reduced-contaminantrenewable feedstock.

A controller to operate a hydrothermal cleaning unit to reduce metalcontaminants in a renewable hydrocarbon feedstock and operate anoil-water separator to separate deionized water from reduced-contaminantrenewable hydrocarbon feedstock at a refinery is also disclosed. In oneembodiment, the controller includes a first input/output in signalcommunication with a flow control valve of a refinery. The flow controlvalve is configured to combine an amount of a water stream containingdeionized water and an amount of a feedstock stream containing acontaminant-rich renewable feedstock to create a mixture of thedeionized water and contaminant-rich renewable feedstock. Here, thecontroller is configured to determine the amount of the water stream tocombine with the feedstock stream, based on a type of contaminant-richrenewable feedstock contained in the feedstock stream. In one or moreembodiments, the controller also includes a second input/output insignal communication with a heat exchanger of the refinery. The heatexchanger is operable to heat the mixture of the deionized water andcontaminant-rich renewable feedstock to a specified temperature. Here,the controller is configured to determine the specified temperaturebased on a first length of time for a hydrothermal reaction. In one ormore embodiments, the controller also includes a third input/output insignal communication with a hydrothermal reactor of the refinery. Thehydrothermal reactor is operable to transfer contaminants in thecontaminant-rich renewable feedstock into the deionized water over thefirst length of time to thereby generate contaminant-rich water and apre-treated renewable feedstock. Here, the controller is configured todetermine the first length of time based on an amount of contaminants inthe contaminant-rich renewable feedstock. In one or more embodiments,the controller also includes a fourth input/output in signalcommunication with an oil-water separator of the refinery. The oil-waterseparator is operable to separate the contaminant-rich water from thepre-treated renewable feedstock over a second length of time. Here, thecontroller is configured to determine the second length of time based onthe amount of contaminants in the contaminant-rich water. In one or moreembodiments, the controller includes a fifth input/output in signalcommunication with a pump configured to raise the pressure of at leastone of the water stream or feedstock stream to an operating pressure.Here, the controller is configured to determine the operating pressurebased on an amount of contaminants in the contaminant-rich renewablefeedstock.

A process for reducing metals contaminants in renewable hydrocarbonfeedstocks at a refinery is also disclosed. In one embodiment, water ispassed through a deionized water generator to generate deionized waterhaving a conductivity of less than about 1 μS/cm. Either the deionizedwater or the pre-deionized water may be passed through an aeration unitto increase the concentration of dissolve oxygen. The aerated, deionizedwater is mixed with a renewable feedstock having hydrocarbon compoundsand metals contaminants to create a deionized water and renewablefeedstock mixture. This mixture is passed into a hydrothermal reactor ata pre-selected temperature, pressure and flow condition. In one or moreembodiments, the flow condition is non-laminar flow having a Reynoldsnumber greater than 2,000. The temperature, pressure and flow conditionof the hydrothermal reactor are maintained for a first interval of timeto transfer at least a portion of the metal contaminants associated withthe renewable feedstock into the aerated, deionized water. After thefirst time interval, the aerated deionized water and renewable feedstockmixture are passed to a separation unit. The aerated, deionized watercontaining the metal contaminants is separated from the renewablefeedstock in the separation unit to create contaminant-rich water and areduced-contaminant renewable feedstock for a second time interval.After the second time interval, the reduced-contaminant renewablefeedstock is passed to a downstream refinery unit for furtherprocessing.

Still other aspects and advantages of these embodiments and otherembodiments, are discussed in detail herein. Moreover, it is to beunderstood that both the foregoing information and the followingdetailed description provide merely illustrative examples of variousaspects and embodiments, and are intended to provide an overview orframework for understanding the nature and character of the claimedaspects and embodiments. Accordingly, these and other implementations,along with advantages and features of the present disclosure hereindisclosed, will become apparent through reference to the followingdescription and the accompanying drawings. Furthermore, it is to beunderstood that the features of the various embodiments described hereinare not mutually exclusive and may exist in various combinations andpermutations.

BRIEF DESCRIPTION OF THE DRAWINGS

Having thus described the disclosure in general terms, reference willnow be made to the accompanying drawings, which are not necessarilydrawn to scale, and wherein:

FIGS. 1-4 are schematic diagrams illustrating refinery systems forremoving inorganic contaminants, including metals, from a renewablehydrocarbon feedstock, according to embodiments of the disclosure;

FIGS. 5A-5C are schematic diagrams illustrating refinery systems forseparating the hydrocarbon feedstock and deionized water mixture thatflows from the hydrothermal reactor, according to embodiments of thedisclosure;

FIGS. 6, 7A, and 7B illustrate features an oil-water separation unit andflow arrangement, according to embodiments of the disclosure;

FIGS. 8-11 are schematic diagrams illustrating additional refinerysystems for removing inorganic contaminants, including metals, from arenewable hydrocarbon feedstock, according to embodiments of thedisclosure;

FIG. 12 is a simplified block diagram illustrating a control system formanaging the removal of inorganic contaminants, including metals, from arenewable hydrocarbon feedstock, according to an embodiment of thedisclosure;

FIG. 13 is a flow diagram, implemented in a controller, for managing theremoval of inorganic contaminants, including metals, from a renewablehydrocarbon feedstock, according to an embodiment of the disclosure; and

FIG. 14 is a diagram illustrating how metal contaminants in thehydrocarbon feedstock may be liberated and transferred into thedeionized water solvent in the hydrothermal reactor, according to one ormore embodiments of the disclosure.

DETAILED DESCRIPTION OF THE DISCLOSURE

So that the manner in which the features and advantages of theembodiments of the systems and methods disclosed herein, as well asothers that will become apparent, may be understood in more detail, amore particular description of embodiments of systems and methodsbriefly summarized above may be had by reference to the followingdetailed description of embodiments thereof, in which one or more arefurther illustrated in the appended drawings, which form a part of thisspecification. It is to be noted, however, that the drawings illustrateonly various embodiments of the systems and methods disclosed herein andare therefore not to be considered limiting of the scope of the systemsand methods disclosed herein as it may include other effectiveembodiments as well.

The present disclosure is directed to refinery systems and methods forthe separation of inorganic contaminants, such as metals and phosphorus,from a hydrocarbon feedstock, including petroleum hydrocarbons andbiomass feedstocks. While typical petroleum-based feedstock may notinclude significant amounts of metal or phosphorus (e.g., the amount ofphosphorus in a petroleum-based feedstock may be undetectable or atabout 1 to 2 parts per million (ppm)), renewable feedstock, however, mayinclude significant amounts metal, phosphorus, and/or other contaminants(e.g., an amount significant enough to cause fouling, coking, catalystdeactivation, or other issues within refinery equipment, such amountbeing in the hundreds to thousands parts per million). Removal of suchmetals, phosphorus, and/or other contaminants may be performed via ahydrothermal cleanup process (e.g., by washing the hydrocarbon feedstockwith water at elevated temperature and pressure via a hydrothermalcleaning unit or hydrothermal reactor). In one or more embodimentsdisclosed herein, an amount of a deionized water may be mixed with therenewable hydrocarbon feedstock and fed to a hydrothermal reactor at aparticular temperature, pressure, turbulent flow and/or time. During theresidence time in the hydrothermal reactor, and while the temperature,pressure, and turbulent flow are maintained, the inorganic contaminantscontained in the renewable hydrocarbon feedstock are liberated andtransferred into the deionized water. The deionized water along with theinorganic contaminants may then be removed from the treated renewablehydrocarbon feedstock through an oil-water separator (e.g., such as aStokes' Law oil-water separator). The separated, contaminant-leanrenewable feedstock may be then passed to downstream refinery processesfor further refinement. The deionized water flowing out of the oil-waterseparator may be saturated with or contain the metal, phosphoruscompounds, salt compounds, and/or other contaminants removed from therenewable feedstock. This deionized water effluent may be treated in anindustrial wastewater treatment system, e.g., to remove the inorganiccontaminants therefrom, as is known to those skilled in the art.

FIGS. 1-4 are schematic diagrams illustrating refinery systems forinorganic contaminant removal from hydrocarbon feedstocks, according toone or more embodiments. In such embodiments, the systems illustrated inFIGS. 1 through 4 may be a part of, included in, disposed at, orintegrated into a refinery. In FIG. 1, a system 100 is illustratedincluding various components. Pipeline, piping, pipes, and/or otherconduit may be disposed throughout the system 100 to convey, transfer,or transport fluids, liquids, gases, and/or solids from one point orlocation within or external to the system 100 to another point orlocation external to or within the system 100. In an example, thepipeline or piping utilized may be anti-corrosive. Due to the corrosivenature of the contaminants in the feedstock (such as free fatty acids)and of the deionized water mixed with the feedstock, the pipeline orpiping may utilize or be constructed of an anti-corrosive material, suchas stainless steel, e.g., 316 stainless steel or 317L stainless steel,or include anti-corrosive coatings. Further, all or some of thecomponents, e.g., the fluid facing components, described herein (e.g.,pumps, flow control valves, heat exchangers, etc.) may be constructed ofsuch anti-corrosive materials or include anti-corrosive coatings, due tothe potentially corrosive nature of the feedstock and of the deionizedwater solvent. Throughout this disclosure, the terms pipeline, piping,pipe, and/or pipes may be used interchangeably.

As illustrated in FIG. 1, a source of water 112 is optionally passedinto a reverse osmosis unit 110 to purify the water. The water fromsource 112 may be a non-deaerated water, such that the water has notbeen deaerated, and thus may contain some gases (e.g., dissolved oxygen,dissolved carbon dioxide, etc.) diffused therein at the source. As iswell known in the art, reverse osmosis units purify water by forcing thewater under pressure through a semi-permeable membrane that permitswater, as well as dissolved oxygen, some ions, and other contaminantssmaller than the membrane pores, to move through the membrane whileretaining solids, including dissolved solids, on the high pressure side(or brine side) of the membrane. The water crossing the membrane (i.e.,permeate) is between about 90% to about 99% free of contaminants. Theextent to which ions and other contaminants are removed (i.e., retainedon the brine side of the membrane) depends on several factors, includingbut not limited to, the operating pressure of the reverse osmosis unit,the feed concentration, the valence of the ions, etc. Thus, the permeatefrom a reverse osmosis unit may continue to have an ion concentration,such that the conductivity of the reverse osmosis water (i.e., thepartially deionized water generated by the reverse osmosis unit 110) maybe between about 5 μS/cm and about 15 μS/cm. In other embodiments, theconductivity may be as high as about 20 μS/cm, about 30 μS/cm or evengreater. In one or more embodiments (not shown), operation of thereverse osmosis may be further enhanced by first passing the water fromits source through a filter, such as a carbon filter, fiber mesh filter,etc., in order to at least partially clean the water prior to beingpassed to the reverse osmosis unit. In one or more other embodiments(not shown), the partially deionized water from the reverse osmosis unitmay be further purified by passing the permeate or deionized waterthrough a filter, such as a carbon filter, fiber mesh filter, etc.

As illustrated in FIG. 1, the partially deionized water from the reverseosmosis unit 110 is then passed to an ion exchange system 120 to furtherpurify the water (e.g., through softening, demineralization, etc.). Asis well known to those skilled in the art, an ion exchange system, in ademineralization application, can function to exchange cations in thewater with hydrogen ions in one bed and exchange anions in the waterwith hydroxyl ions in another bed. After all of the cations and anionsin the water (i.e., minerals and contaminant ions/molecules) have beenexchanged, the resulting deionized water from the ion exchange system120 has remaining ions on the order of less than parts per millions oreven billions. The conductivity of such deionized water (generated fromthe ion exchange system 120) can be much less than the conductivityresulting from a reverse osmosis unit. In one or more embodiments, thedeionized water from an ion exchange system 120 may be less than about10 μS/cm, less than about 5 μS/cm, less than about 3 μS/cm, less thanabout 1 μS/cm, less than about 0.5 μS/cm or even less.

While FIG. 1 shows the use of a reverse osmosis unit 110 positionedupstream of the ion exchange system 120, the treatment of water byreverse osmosis is optional, as previously noted. Thus, in embodimentsin which a reverse osmosis unit is not employed, the water from thesource 112 is passed directly to the ion exchange system 120. In one ormore other embodiments (not shown), the water from source 112 is passedthrough a carbon black filter, fiber mesh filter, or other type ofmechanical filter known to those skilled in the art prior to beingpassed to the ion exchange system 120. In one or more other embodiments(not shown), a reverse osmosis unit may be used in place of an ionexchange system, for example, to produce a partially deionized water formixing with the hydrocarbon feedstock.

Deionized water is known as a universal solvent. It is highly corrosiveto carbon steel, copper, and other types of metals, as is known to thoseskilled in the art. Because deionized water lacks buffering ions, suchas the metal ions (e.g., calcium ions, iron ions, sodium ions, etc.)removed during ion exchange, the deionized water has an affinity formetal ions as buffering ions and readily attracts metal ions therein.Thus, when deionized water encounters metals that are susceptible tocorrosion, the deionized water is believed to act a driving force tofurther the corrosion or oxidation of the metals thereby liberatingmetals to be transferred into the deionized water as ions. The deionizedwater may further cause the dissociation of existing ionic bonds ofmetal compounds, such that the metal ions are transferred into thedeionized water. In one or more embodiments, the materials ofconstruction of the various piping and/or refinery equipment areselected to reduce the corrosion due to the deionized water generated bythe ion exchange system 120. According to ASTM D1193-91, there arevarious levels of purity or types of deionized water. In one or moreembodiments of this disclosure, the deionized water used is of Type IV,and has a resistivity (Ω-cm) of between about 4 and about 0.2, aconductivity (μS/cm) of between about 0.25 and about 5, a pH at 25° C.of between about 5.0 and about 8.0, a sodium concentration of <50 ppb,and a chloride concentration of <50 ppb. In one or more otherembodiments, deionized water or pure water of Types I, II, or III,according to ASTM D1193-91, may be used. For instance, Type III may beused and has a resistivity (Ω-cm) of greater than about 4, aconductivity (μS/cm) of less than about 0.25, a total organic carbon ofless than about 200, a sodium concentration of <10 ppb, a chlorideconcentration of <10 ppb, and a silica concentration of <500 μg/L. Thus,in one or more embodiments of the system and method disclosed herein,the deionized water used, whether generated by a reverse osmosis unit,an ion exchange system, or both in tandem, has a conductivity atgeneration of less than about 5 μS/cm, less than about 3 μS/cm, lessthan about 2 μS/cm, less than about 1 μS/cm, less than about 0.8 μS/cm,less than about 0.6 μS/cm, less than about 0.5 μS/cm, less than about0.4 μS/cm, less than about 0.25 μS/cm, or even less.

The deionized water generated at ion exchange system 120 is passed toand becomes feed for pump 142. While not shown in FIG. 1, a tank orother vessel may be positioned in fluid communication between the ionexchange system 120 and pump 142, such that an adequate amount ofdeionized fluid is readily available for pump 142. Pump 142 pumps thedeionized water through a heat exchanger 144 and to a mixer 140. Inaddition to driving the deionized water through the associated piping,pump 142 may pressurize the deionized water to the operating pressure ofthe hydrothermal reactor 150, which will be further described below. Theheat exchanger 144 may heat the deionized water to the operatingtemperature of the hydrothermal reactor 150. Heat exchanger 144 permitsheat to be transferred and added to the deionized water stream from adedicated hot fluid stream (e.g., steam) and/or through heat integrationfrom a hot process fluid stream, as is well known to those skilled inthe art. The heated and pressurized deionized water is fed or passed toa mixer 140, which may be a mixing valve, in-line mixer, or other devicethat allows two fluid streams to be combined and/or mixed to create asingle fluid outlet stream.

In one or more embodiments, a weak acid, such as citric acid, aceticacid, etc., may be added to or injected into the deionized water priorto mixing with the hydrocarbon feedstock in mixer 140. One benefit of alower conductivity deionized water is that the addition of acid to thedeionized water may be reduced as compared to a higher conductivitydeionized water. With respect to a lower conductivity deionized water,the acid has a more pronounced effect because of the lack ofions/buffering ions in the lower conductivity water. Thus, with lowerconductivity, e.g., less than 1 μS/cm, less than 0.5 μS/cm, or evenlower, less acid will be needed to facilitate liberation of metals andother inorganic compounds in the hydrocarbon feedstock (e.g., throughcorrosion, etc.), as described further below.

As further illustrated in FIG. 1, a hydrocarbon feedstock is procuredvia stream 132 and is passed to tank or other vessel 130 for holdingand/or storage. The hydrocarbon feedstock is as described above and maybe a petroleum hydrocarbon or a biomass/renewable hydrocarbon. Thehydrocarbon feedstock entering tank 130 via stream 132 has inorganiccontaminants, including metals and/or phosphorus, to be removed prior tofurther refinery processing. Pump 146 pumps the fluid hydrocarbonfeedstock from tank 130 to and through a heat exchanger 148 and to themixer 140. In addition to driving the fluid hydrocarbon feedstockthrough the associated piping, pump 146 may pressurize the hydrocarbonfeedstock to the operating pressure of the hydrothermal reactor 150,which will be further described below. The heat exchanger 148 may heatthe hydrocarbon feedstock to the operating temperature of thehydrothermal reactor 150. Heat exchanger 148 permits heat to betransferred and added to the hydrocarbon feedstock stream from adedicated hot fluid stream (e.g., steam) and/or through heat integrationfrom a hot process fluid stream, as is well known to those skilled inthe art. The heated and pressurized hydrocarbon feedstock is fed orpassed to the mixer 140. In mixer 140, the hydrocarbon feedstock and thedeionized water are mixed to create a deionized water and hydrocarbonfeedstock mixture. In one or more embodiments, the deionized water ismixed with the hydrocarbon feedstock such that the deionized water is atleast 10%, at least 15%, at least 20%, at least 25%, at least 30%, atleast 35%, at least 40%, at least 45%, at least 50%, at least 55%, atleast 60%, at least 65% or even more by volume of the total mixture ofdeionized water and hydrocarbon feedstock. In one or more embodiments,the deionized water is at least one-third by volume of the total mixtureof deionized water and hydrocarbon feedstock. In one or more otherembodiments, the deionized water is at least half by volume of totalmixture of deionized water and hydrocarbon feedstock.

The hydrothermal reactor 150 is arranged to receive the mixture ofdeionized water and hydrocarbon feedstock. The reactor 150 may be acontinuous stirred tank reactor, plug flow reactor, or other type ofreactor known to those skilled in the art to permit the mixture to flowtherein for a residence time at a specified temperature and pressure. Inone or more embodiments, the reactor 150 may be a combination ofcontinuous stirred tank reactors, plug flow reactors or a combination ofboth. The liberation of metals and/or other inorganic contaminants fromthe hydrocarbon feedstock (e.g., oils) may be accomplished at elevatedtemperature and pressure. In one or more embodiments, the temperature ofthe reactor 150 may be maintained between about 200° C. and about 500°C. In one or more embodiments, the temperature of the reactor 150 may bemaintained between about 200° C. and about 450° C., between about 200°C. and about 400° C., between about 200° C. and about 350° C., or evenbetween about 200° C. and about 300° C. The heat exchangers 144, 148 maybe arranged to deliver the deionized water and hydrocarbon at thespecified operating temperature of the reactor 150. In one or moreembodiments, the pressure of the reactor 150 may be maintained betweenabout 500 psig to about 6,000 psig. In one or more other embodiments,the pressure of the reactor 150 may be maintained between about 1,000psig and about 1,500 psig. In one or more other embodiments, thepressure of the reactor 150 may be maintained between about 2,000 psigand about 3,500 psig. In one or more embodiments, the pressure may bespecified to maintain the mixture (or portions thereof) in a liquidphase, in a vapor-liquid phase or in a partial or full supercriticalphase. In one or more embodiments, the flow of the mixture in thereactor is non-laminar flow. Laminar flow is typically flow that has aReynolds number less than 2,000. In those embodiments in whichnon-laminar flow is maintained through the reactor, the Reynolds numberis greater than 2,000, such that the flow may be considered turbulent orin transition to turbulent flow.

The temperature, pressure, and flow (laminar versus non-laminar) arespecified to reduce rearrangement reactions involving the hydrocarbonchains of the hydrocarbon feedstock. In other words, the temperature,pressure and non-laminar flow are selected to wash and liberateinorganic contaminants from the hydrocarbon feedstock but not causecracking, isomerization or similar reactions involving the hydrocarbonchains of the hydrocarbon feedstock. In one or more embodiments, theresidence time or time interval in which the mixture resides within thereactor may be between about 30 seconds to about 5 minutes or evenbetween about 1 minute and about 4 minutes. In one or more otherembodiments, residence time may be longer, especially at reducedtemperature and pressure, such that the time may be as much as 6minutes, 7 minutes, 8 minutes, 9 minutes, or even 10 minutes.

Turning now to FIG. 14, a plug flow reactor 1410 is illustrated. Amixture of deionized water and hydrocarbon feedstock flow through thereactor 1410 from left to right. As represented by the curved arrows,the flow of the mixture may be considered to be non-laminar orturbulent, having a Reynolds number greater than 2,000. Dotted line box1430 represents deionized water within the mixture that has dissolvedoxygen associated therewith. Dotted line box 1420 represents hydrocarbonfeedstock with an associated metal contaminant illustrated by theoctagon. The dissolved oxygen in the deionized water 1430 is believed toreact with the metal particle at 1424 to generate water H₂O from theoxygen O₂. To form the water H₂O, hydrogen ions H⁺ from the aqueousfluid (e.g., carbonic acid in the deionized water) are contributed tothe oxygen O₂ as well as electrons e⁻, which are contributed by themetal itself from a point 1422. As shown in FIG. 14, point 1424 servesas the cathode while point 1422 serves as the anode. At the anode 1422,the metal is removed into the aqueous fluid (i.e., deionized water) aspositive metal ions as elections e⁻ are removed from the metal andtransferred to the cathode as shown. The remaining metal becomes pittedas metal is removed as aqueous metal ions. As previously described, thepositive metal ions liberated from the metal particle associated thehydrocarbon feedstock are believed to have an affinity for and areattracted to the deionized water 1432, which seeks the metal ions (showncollected within the deionized water at 1432) as buffering ions.

While the representation illustrated in FIG. 14 provides some insightinto how the deionized water, and dissolved oxygen therein, may act toenhance metal liberation and transfer from the hydrocarbon feedstockinto the deionized water, other actions and methods of electrochemicalreaction and/or metal liberation/transfer as they may occur are not tobe precluded by this sole representation and are understood to beincluded herein. For example, and not to be limiting, the dissolvedoxygen may further combine with positive metal ions to create metaloxides. Further still, the deionized water may hasten the dissociationof ionic bonds involving metal compounds, thereby releasing metal ionsthat are then attracted by and concentrated in the deionized water. Inany case, the use of deionized water in place of non-deionized water inthe hydrothermal reactor increases the liberation and transfer of metalsfrom the hydrocarbon feedstock to the deionized water for removal. And,as the conductivity of the deionized water becomes lower, e.g., lessthan 3 μS/cm, less than 1 μS/cm, less than 0.8 μS/cm, or even lower, theliberation and transfer of metals from the hydrocarbon feedstock to thedeionized water may increase, and thereby be enhanced.

After the mixture has flowed through or within the reactor 150 for theresidence time, the mixture exits the reactor 150 and is passed viapiping to a heat exchanger 162 to recover heat from the mixture, therebycooling the mixture. This piping transports the effluent or pre-treatedfeedstock (e.g., pre-treated by the hydrothermal reactor 150) from thehydrothermal cleaning unit or hydrothermal reactor 150 through the heatexchanger 162 and through a flow control valve 164 to an oil-waterseparator 170 (e.g., a Stokes' Law separator). As noted, effluent mayrefer to the liquid or pre-treated feedstock output from thehydrothermal cleaning unit or hydrothermal reactor 150. The liquid mayinclude a blend of water and feedstock, with the water including theinorganic contaminants (e.g., metals, phosphorus, etc.) washed from thefeedstock in the hydrothermal cleaning unit or hydrothermal reactor 150.The flow control valve 164 may lower or drop the pressure of theeffluent, at which point the effluent may be considered influent (e.g.,influent into the oil-water separator 170). The influent may refer tothe pre-treated feedstock entering the oil-gas separator, for which thepre-treated feedstock may exhibit a change or alteration (e.g., pressuredrop, temperature change, added water, and/or added chemicals). Theinfluent, with a lower pressure than the effluent, may then betransported or transferred to an oil-water separator 170 (e.g., aStokes' Law separator, crude desalter unit including an electrostaticprecipitator, etc.). In such examples, the pressure of the effluent inpiping (upstream of the flow control valve 164) may be higher than theoperating pressure of the oil-water separator 170. As such, the flowcontrol valve 164 may lower the pressure to within the range ofoperating pressures of the oil-water separator 170. The oil-waterseparator 170 may separate the deionized water from the hydrocarbonfeedstock. The deionized water may be collected at a point at or alongthe bottom of the oil-water separator 170 and be drained therefrom foranother use or for wastewater treatment at point 172. The oil-waterseparation unit 170 and associated equipment may be included at orintegrated into a refinery. The remaining treated hydrocarbon feedstockmay be transported from the oil-water separator 170 via piping 174 to adownstream refinery process unit 180, to a tank, to a feed drum forfurther transfer of feedstock to a reactor, or other component/equipmentwithin the refinery. The oil-water separator 170 may be a largeseparator (for example, a Stokes Law separator), which is used to removewater from the pre-treated hydrocarbon feedstock downstream of thehydrothermal cleaning unit or hydrothermal reactor 150. In suchexamples, the large separator may not be typical for a refinery and maytake up large amounts of space, thus increasing overall refineryoperation costs and decreasing available real estate for other processesand/or equipment. Further, such a separator may not completely removethe water from the pre-treated hydrocarbon feedstock from thehydrothermal cleaning unit or hydrothermal reactor 150 (e.g., such aseparator may remove all but 1.5%, 2%, 4%, or even 6% of water from thepre-treated hydrocarbon feedstock). Further still, such a separator maytake longer periods of time (e.g., hours rather than minutes) to removethe water, as such a separator may rely on time for the feedstock andwater to naturally separate or settle. In one or more embodiments, theresidence time within such a large Stokes' Law separator may be from 60to 180 minutes, from 90 to 150 minutes, or even as long as 4, 5 or 6hours.

Rather than utilizing the large separator described above, thisdisclosure also describes the use of a crude desalter unit and/orelectrostatic precipitation unit, which despite expectations, has beendiscovered to efficiently remove or separate water from effluent,pre-treated hydrocarbon feedstock, or feedstock (e.g., feedstockcontaining high levels of metal and/or phosphorus). Typically,refineries include a crude desalter unit and/or electrostaticprecipitation units, thus decreasing the need for new equipment. Byincreasing the amount of water (e.g., fresh water, deionized water orwater fed back from the crude desalter unit or electrostaticprecipitation unit) in the effluent or pre-treated hydrocarbon feedstockif the effluent or pre-treated feedstock does not include enough water,the crude desalter unit or electrostatic precipitation unit may beoperated to properly remove the water from the effluent or pre-treatedhydrocarbon feedstock. Further, the amount of water to be mixed with theeffluent or pre-treated hydrocarbon feedstock may vary based on the typeof feedstock and the amount of metal and/or salt in the hydrocarbonfeedstock (for example, choice white grease may include lesscontaminants than packers tallow and thus require less water for removalof contamination). In another example, the amount of water in theeffluent or pre-treated hydrocarbon feedstock may be sufficient for thecrude desalter unit or electrostatic precipitation unit to be operatedto properly remove the water from the effluent or pre-treatedhydrocarbon feedstock. As used herein, effluent may refer to the liquidor pre-treated hydrocarbon feedstock output from the hydrothermalcleaning unit or hydrothermal reactor 150. Further, effluent may be usedinterchangeably with pre-treated hydrocarbon feedstock throughout. Atthe point that water and/or chemicals are added to the effluent, theeffluent may be considered influent. Further, the amount of electricityutilized in a crude desalter unit and/or electrostatic precipitator mayvary depending on the hydrocarbon feedstock. For example, the amount ofelectricity utilized may be based on the conductivity of the effluent orpre-treated hydrocarbon feedstock (e.g., the lower the conductivity ofthe effluent or pre-treated hydrocarbon feedstock, the larger or higheramounts of electricity which may be utilized to induce separation ofwater and hydrocarbon feedstock/oil). Thus, via the use of an existingcrude desalter unit and/or electrostatic precipitator, more water (e.g.,the contaminant-rich water) may be removed (for example, from about1.5%, 2%, 4%, or even 6% water leftover when utilizing a large separatordown to about 0.7%, 0.5% or even 0.3% of water leftover when utilizing acrude desalter unit and/or electrostatic precipitator) using less space,less time, existing refinery equipment, and a reduced cost.

Turning now to FIG. 2, the system of enhancing the removal of metalcontaminants from a hydrocarbon feedstock is similar to that shown in,and described with respect to, FIG. 1. A main difference to the system101 of FIG. 2 is the addition of an aeration unit 122 proximate the ionexchange system. As shown, aeration unit 122 is position downstream ofthe ion exchange system 120 but upstream of the pump 142. The aerationunit 122 may be any industrial aeration unit known to those skilled inthe art that imparts oxygen (e.g., from air) into water as dissolvedoxygen. Such aeration unit 122 may be selected from various types ofwater fall aerators (e.g., tray aerators, forced draft aerators, etc.)and/or air diffusion aerators. A benefit of the aeration unit 122positioned after the ion exchange system is that the air dissolved inthe deionized water creates a slightly acidic deionized water due to thecarbon dioxide in the air (e.g., forming carbonic acid in the deionizedwater). A slightly acidic deionized water may provide added benefits inliberating metals from the hydrocarbon feedstocks in reactor 150. In oneor more embodiments, and as described above, a weak acid, such as citricacid, acetic acid, etc., may also be added to the deionized water priorto mixing with the hydrocarbon feedstock in mixer 140. In one or moreembodiments, the aeration unit 122 is positioned upstream of the ionexchange system 120 or even upstream of the optional reverse osmosisunit 110. Because at least a portion of the dissolved oxygen (as well ascarbon dioxide and other dissolved gases) added by the aeration unitpasses through the semi-permeable membrane of the reverse osmosis unit110 and is not exchanged with hydrogen or hydroxyl ions in the ionexchange resin of ion exchange system 120, the aeration unit 122 may bepositioned in several locations upstream of pump 142. In one or moreother embodiments (not shown), a reverse osmosis unit along with anaeration unit may be used in place of an ion exchange system, forexample, to produce aerated, partially deionized water for mixing withthe hydrocarbon feedstock. While a slightly acidic deionized water isbeneficial, the increased concentration of dissolved oxygen may also beof benefit. As described above, dissolved oxygen is believed tocontribute to a greater electrochemical reaction with the metals of thehydrocarbon feedstock in the reactor 150. Therefore, an increasedconcentration of dissolved oxygen in the deionized water may furtherincrease the liberation and transfer of metals to the deionized waterwithin the reactor.

Turning now to FIG. 3, a similar system 200 to that of FIG. 1 isillustrated. Here, the last two digits of the reference numbers areintended to identify identical or similar items as in FIGS. 1 and 2. Asshown in FIG. 3, a second pump 245 draws deionized water from a tank orvalve 224 in fluid communication with the ion exchange system 220. Pump245 transfers deionized water for injection at junction or flow controlvalve 268 into the effluent from the hydrothermal reactor 250. As notedabove, the effluent from the hydrothermal reactor 250 becomes theinfluent to the oil-water separator 270. The addition of deionized waterinto this effluent/influent stream may further increase the liberationof metals from the pre-treated hydrocarbon feedstock, e.g., in theoil-water separator and/or in the piping leading thereto. Turning now toFIG. 4, a similar system 201 to that of FIG. 2 and FIG. 3 isillustrated. Here, the last two digits of the reference numbers areintended to identify identical or similar items as in FIGS. 1-3. Asshown in FIG. 4, the system 201 includes an aeration unit 222 positionedbetween and in fluid communication with the ion exchange system 220 andthe tank/valve 224. The aeration unit 222 increases the amount orconcentration of dissolved air, and thus dissolved oxygen, in thedeionized water that is fed to the hydrothermal reactor 250 via pump 242and to the oil-water separator 270 via pump 245.

FIGS. 5A to 5C are schematic diagrams illustrating refinery systems forseparating the hydrocarbon feedstock and deionized water mixture thatflows from the hydrothermal reactor, according to embodiments of thedisclosure. In FIG. 5A, the system 500 may include a flow control valve564 that is fed by effluent stream 560. The flow control valve 564reduces the pressure of the effluent stream 560 to the operatingpressure of the oil-separator 570. The mixture of deionized water andhydrocarbon feedstock is passed to the oil-separator 570 (e.g., aStokes' Law separator), where the deionized water along with metals andother inorganic contaminants settle to the bottom and are recoveredthrough stream 572 for subsequent wastewater treatment. The pre-treatedhydrocarbon feedstock (e.g., oils) rises to the top of the oil-separator570, where it is skimmed and/or otherwise collected and passed to ahydroprocessing unit 580, or other downstream refinery unit/process. InFIG. 5B, heat exchanger 566 is positioned downstream of flow controlvalve 564 to cool (or heat) the effluent to a lower (or higher)temperature (at which point the effluent may be considered influent),before transportation to the oil-water separation unit 570. In one ormore embodiments, and especially if the effluent stream is to be cooled,the heat exchanger 566 may be positioned upstream of the flow controlvalve 560 in order to better capture the heat transfer (versus firstthrottling through flow control valve 546 creating Joule-Thompsoncooling). In one or more embodiments, a sensor may be disposed at theheat exchanger 566, at the flow control valve 564, and/or at some pointbetween the flow control valve 564 and heat exchanger 566. The heatexchanger 566 may heat or cool the effluent to a specific temperature,based on the actual temperature of the effluent as measured by thesensor. For example, if the effluent is at the operating temperature ofthe oil-water separation unit 570 such that the water may be removed orseparated from the hydrocarbon feedstock, then the heat exchanger 566may not heat or cool the effluent, otherwise the effluent may be heatedor cooled. In other words, the effluent from a hydrothermal reactor (notshown) may be sufficiently heated or cooled for use in the oil-waterseparation unit 570. In another example, the operating temperature ofthe hydrothermal reactor or hydrothermal cleaning unit may be about 465°F. to about 575° F. Further, the operating temperature of the oil-waterseparation unit 570 (e.g., a crude desalter unit including anelectrostatic precipitator) may be about 100° F. to about 300° F. Insuch examples, as the effluent leaves the hydrothermal reactor orhydrothermal cleaning unit, the effluent may be at a temperature abovethe operating temperature of the oil-water separation unit 570. Furtherstill, the heat exchanger 566 may cool the effluent to the operatingtemperature. In such examples, the heat exchanger 566 may be a fin fancooler or another type of heat exchanger to cool liquid, as will beunderstood by those skilled in the art.

In FIG. 5C, the system may include a junction or flow control valve 568to increase the amount of deionized water or chemicals added to theeffluent prior to entering the oil-water separation unit 570. In anotherexample, junction or flow control valve 568 may be a mixing valve or anin-line mixer to mix the effluent with other liquids, at which point theeffluent may be considered influent. In another example, a separatein-line mixer may be disposed after junction or flow control valve 568to mix any additional liquids with the effluent. A certain amount ofdeionized water in comparison to the pre-treated hydrocarbon feedstockmay be further added to increase the removal of inorganic contaminants(metals and/or salt). The amount of deionized water utilized in thehydrothermal cleaning process may or may not be enough water for theoil-water separation unit 570 (e.g., an electrostatic precipitator orcrude desalting process, in particular, due to the addition of otherinorganic materials other than the typical salt compounds). In suchexamples, more deionized water may be added to the effluent at thejunction or flow control valve 568, at which point the effluent may beconsidered influent. The deionized water may be added via pipeline orpiping 565, via junction or flow control valve 567, from the samedeionized water source (see FIGS. 3 and 4) used for the hydrothermalcleaning process or from a different source. Another source of water maybe recycled water from the oil-water separation unit 570, which may beadded at junction or flow control valve 567 via junction or flow controlvalve 569. The total amount of water (e.g., deionized water) used in theratio of water to feedstock may be anywhere from about 10% to about 50%of the total (e.g., about 15% water to about 85% feedstock). In anotherexample, the amount of water in the effluent may be sufficient for theStokes' Law separator or electrostatic precipitation unit 570 (e.g., theeffluent may include about 10% to 50% water).

In another example, the effluent may be completely emulsified. In suchexamples, an amount of chemicals (for example, demulsifiers ordemulsifying agents) may be added to or injected into the effluent atjunction or flow control valve 567, at which point the effluent may beconsidered influent. Small amounts of the chemicals may be added in orinjected into the effluent to aid in the breaking of the emulsion. Suchchemicals may include Truscent Ascent 840, Truscent Ascent 850, BakerHughes Xeric 7010, and/or other demulsifying chemicals as will beunderstood by those skilled in the art. In another example, thechemicals may be mixed with water at junction or flow control valve 567and then mixed with the effluent at junction or flow control valve 568.Upon separation of the influent, the chemicals may be contained in thewater.

In FIG. 6, the system 600 is illustrated with effluent or influent(which may or may not include extra deionized or non-deionized water)flowing through the pipeline or piping 660 to flow control valve 664.The flow control valve 664 may decrease the pressure of the effluent orinfluent from a pre-treatment unit (e.g., a hydrothermal cleaning unitor hydrothermal reactor). The pressure in the pre-treatment cleaningunit and in the pipeline or piping 664 may be considerably higher thanthe operating pressure of an oil-water separation unit 670 having anelectrostatic precipitator 671. For example, the pressure of theeffluent or influent in piping 660 may be at about 1500 pounds-force persquare inch gauge (psig), while the operating pressure of the oil-waterseparation unit 670 may be about 150 to about 250 psig. As such, thesystem may include a flow control valve 664 to lower or drop thepressure of the effluent or influent in pipeline or piping 660. Thesystem may also include a heat exchanger 666 to heat or cool theeffluent or influent, depending on the temperature of the effluent orinfluent and the operating temperature of the oil-water separation unit670 housing electrostatic precipitator 671.

In another example, the oil-water separation unit 670 may include anelectrostatic precipitator 671 having grid-like structure of electrodes.The electrodes may be connected to a power source 673. The power source673 may provide power to the electrodes of the electrostaticprecipitator 671 (e.g., as an alternating or direct current or avoltage). The power source 673 may be a transformer to step up a voltagefrom the grid or another refinery power source. For example, thetransformer may connect to a 460-volt power source (e.g., from a utilitycompany, the grid, an off grid power source, an off-grid power sourcededicated to the refinery, or another refinery power source). Thetransformer may step the voltage up to about 20 thousand volts to 30thousand volts, depending on the conductivity of the influent. As theinfluent (which may or may not include extra water and/or chemicals) ispumped into the oil-water separation unit 670, power may be provided tothe electrodes of the electrostatic precipitator 671, which may createan electrostatic field within the influent. In such examples, theelectrostatic field may polarize the water droplets floating in thelarger volume of feedstock. The water droplets may clump together andsettle near the bottom of the oil-water separation unit 670. The watermay then be drained off at pipeline or piping 672. Further and asdescribed throughout, the temperature of the liquid inside the oil-waterseparation unit 670 may affect the separation of the water from thefeedstock. Further still, the pressure within the oil-water separationunit 670 may affect the separation of the water from the feedstock (forexample, the pressure within the oil-water separation unit 670, forseparation, may be about 150 psig to about 250 psig). Thede-contaminated or reduced-contaminant feedstock may then betransferred, via pipeline or piping 674, to a fractional distillationcolumn 680, a tank, to another component or equipment within a refinery,to a feed drum for further transfer of feedstock to a reactor, and/orfor mixing with other de-contaminated feedstock.

In another example, the system may include several junctions or flowcontrol valves to control the addition or injection of deionized water,non-deionized water, and/or chemicals. As noted above, the junctions orflow control valves may be mixing valves or include in-line mixers. Forexample, the water including the contaminants may be drained from theoil-water separation unit 670 to junction or flow control valve 669.Depending on whether water is to be recycled back through the system,the water may flow to junction or flow control valve 667 or via pipelineor piping 672 to be stored or treated. At junction or flow control valve667, depending on various factors (e.g., how emulsified the effluent isor how much water the effluent contains), chemicals (e.g., demulsifyingchemicals or agents), fresh water (deionized or non-deionized) orrecycled water may be mixed and/or transported to junction or flowcontrol valve 668 to be added into the effluent, at which point theeffluent may be considered influent.

An example of an electrostatic precipitation oil-water separation unit700 is illustrated in FIGS. 7A and 7B. In an example, the electrostaticprecipitation unit 700 may include a vessel 702 or enclosure to holdinfluent 728 or any other type of oil/water mixture (e.g., a pre-treatedfeedstock which may or may not include additional water and/orchemicals). Disposed within the vessel 702 may be several layers ofelectrodes 704, 705, 707 (e.g., a bottom layer of electrodes 704, amiddle layer of electrodes 705, and a top layer of electrodes 707). Theelectrodes 704, 705, 707 may connect to a transformer 706 via insulatedcable 722. The insulated cable 722 may be insulated to prevent or reducerisk of electrocution, short circuit, and/or arc faults. The transformer706 may connect to an external power source, as noted above. In otherwords, the transformer 706 may transfer or provide power or a highvoltage (e.g., about 20 thousand to about 30 thousand volts) to theelectrodes 704, 705, 707.

The electrostatic precipitation unit 700 may include various pipelinesor piping to receive an influent flow and transport separated oil 720and separated contaminant rich water 718. For example, a pipeline orpiping 708 may pass through the bottom of the electrostaticprecipitation unit 700 to provide an influent flow to the electrostaticprecipitation unit 700. The influent flow may flow through pipeline orpiping 708 to flanges 710. The flanges 710 may include apertures oropenings to allow the influent 728 (e.g., the influent comprised ofeffluent from a hydrothermal reactor and/or including additional waterand/or chemicals) to pass, flow, or spray through the to the inside ofthe vessel 702. The influent 728 may pass, flow, or spray through theapertures or openings and contact the electrodes 704, 705, 707. In suchexamples, the electrodes 704, 705, 707 may create an electrostatic fieldvia the voltage provided by the transformer 706 via insulated cables722. The electrostatic field created by the electrodes 704, 705, 707 mayinduce polarization of the contaminant rich water 718 inside theinfluent 728 causing the influent 728 to separate into the contaminantrich water 718 and oil 720 (e.g., the de-contaminated or reducedcontaminant feedstock). The contaminant rich water 718 may then collect,clump, settle, or pool at the bottom of the vessel 702 and drain throughnotches, openings, or apertures 726 in pipeline or piping 716, while theseparated oil 720 may pass through openings or apertures 724 in pipelineor piping 712. In an example, the process of separating the oil 720(e.g., feedstock) from the contaminant rich water 718 in the influent728 may be performed in about 10 minutes to about 60 minutes. Thepipeline or piping 712 may transport the oil 720 to other refineryprocesses and/or equipment. The pipeline or piping 716 may transport thecontaminant rich water 718 to a junction or flow control valve forre-use in the electrostatic precipitation unit 700 or in other refineryprocesses or for treatment at a wastewater treatment unit or facility(e.g., at or separate from the refinery).

In FIG. 8, the system 800 may include two or more tanks. The system 800may include a feedstock tank 830 (or other source of feedstock), a watertank 824 (or other water source), other tanks to store other feedstockand/or additional water, and/or connections to feedstock and/or watersources (e.g., deionized water sources). The system may further includea connection to another water source.

Each tank may connect to a pump 842, 845, 846 and/or a heat exchanger844, 848. The pumps 842, 846 may increase the pressure of the feedstockand/or water to the operating pressure of the hydrothermal reactor 850.In another example, the water may be injected into the feedstock (forexample, at junction or flow control valve 840) and then passed to apump (not shown) and/or heat exchanger 852. In such examples, the mixedor blended feedstock and water (e.g., deionized water), the feedstock,and/or the deionized water may be heated, via the heat exchanger 844,848, 852 to a temperature sufficient for the water to absorb the metals,phosphorous, and/or other contaminants. In such examples, the blend oreach portion of the blend (i.e., the water and/or feedstock) may beheated to about 465° F. to about 575° F.

In another example, the heated hydrocarbon feedstock and deionized watermixture may be passed to the hydrothermal reactor 850. In such examples,the hydrothermal reactor 850 may have one or more long tube-likestructures to provide sufficient residence time (e.g., about 30 secondsto 5 minutes) at the sufficient temperature to wash the contaminantsfrom the hydrocarbon feedstock into the deionized water. In an example,such a process may utilize about 10% to about 50% water (the amount ofwater relative to the total amount of water and feedstock). For example,to process approximately 40 thousand barrels of oil per day (MBD) offeedstock the hydrothermal reactor 850 may utilize approximately 12 MBDof deionized water or 350 gallons per minute (GPM) of deionized water.

Once the contaminants have been washed from the hydrocarbon feedstockinto the deionized water, the feedstock and water mixture may betransported to a heat exchanger 862 to reduce the temperature of themixture (based on the temperature of the mixture entering the heatexchanger 862). Downstream of the heat exchanger 862, the mixture passesthrough a flow control valve 864 to decrease the pressure of themixture. From the flow control valve, the mixture may be transported tothe electrostatic precipitation unit 870. In another example, the amountof deionized water in the blend or mix of hydrocarbon feedstock anddeionized water may not include an amount of water sufficient toseparate the water from the feedstock via the electrostaticprecipitation unit 870. In such examples, extra or additional freshwater (e.g., deionized water) from the deionized water tank 824 may beadded from deionized water tank 824, via pump 845 and via junctions orflow control valves 867, 868, to the mixture/influent. In one or moreembodiments, recycled water drained from the electrostatic precipitationunit 870 may be added to the mixture/influent via junctions or flowcontrol valves 867, 868, 869. The mixture or combined mixture andadditional water may be transported to the electrostatic precipitationunit 870, where all or most of the water (for example, all but about0.7%, about 0.5% or even about 0.3% of the water) may be separated in ashort period of time (e.g., about 10 minutes to about 60 minutes). Thewater containing the contaminants may be transported, via pipeline orpiping 872 from the electrostatic precipitation unit 870, while thefeedstock may be transported to a tank, a refinery process or component,a fractional distillation column, to a point where the pre-treatedhydrocarbon feedstock may be combined with another feedstock, to a feeddrum for further transfer of pre-treated hydrocarbon feedstock to areactor, and/or other points or locations within or external to therefinery, e.g., for processing through various refinery operations.

As illustrated in FIG. 9, the system 900 may include a controller 906.The controller 906 may connect to or be in signal communication withvarious different sensors, other controllers, meters, or components inthe refinery. In another example, the controller 906 may be a refinerycontroller and may include instructions, in addition to the instructionsdescribed below, to control various refinery processes and/or equipment.The controller 906 may include memory and one or more processors. Thememory may store instructions executable by the one or more processors.In an example, the memory may be a machine-readable storage medium. Asused herein, a “machine-readable storage medium” may be any electronic,magnetic, optical, or other physical storage apparatus to contain orstore information such as executable instructions, data, and the like.For example, any machine-readable storage medium described herein may beany of random access memory (RAM), volatile memory, non-volatile memory,flash memory, a storage drive (e.g., hard drive), a solid state drive,any type of storage disc, and the like, or a combination thereof. Asnoted, the memory may store or include instructions executable by aprocessor. As used herein, a “processor” may include, for example oneprocessor or multiple processors included in a single device ordistributed across multiple computing devices. The processor may be atleast one of a central processing unit (CPU), a semiconductor-basedmicroprocessor, a graphics processing unit (GPU), a field-programmablegate array (FPGA) to retrieve and execute instructions, a real timeprocessor (RTP), other electronic circuitry suitable for the retrievaland execution instructions stored on a machine-readable storage medium,or a combination thereof.

As used herein, “signal communication” refers to electric communicationsuch as hard wiring two components together or wireless communication,as understood by those skilled in the art. For example, wirelesscommunication may be Wi-Fi®, Bluetooth®, ZigBee, or forms of near fieldcommunications. In addition, signal communication may include one ormore intermediate controllers or relays disposed between elements thatare in signal communication with one another.

In such examples, the controller 906 may determine whether to and/or towhat temperature the hydrocarbon feedstock, deionized water, and/oreffluent may be heated or cooled. The controller 906 may make suchdeterminations based on the type of feedstock, the initial temperatureof the hydrocarbon feedstock, the initial temperature of the deionizedwater, the temperature of the effluent exiting the hydrothermal reactor950, and/or the temperature of deionized or other water to be added tothe effluent, e.g., via pump 945. Such data may be provided via sensorsdisposed throughout the system 900, as shown. Similarly, controller 906may determine to what pressure the hydrocarbon feedstock, deionizedwater, and/or effluent are to be pressurized to or depressurized fromvia pumps 942, 946 and flow control valve (e.g., letdown valve) 964,respectively. The controller 906 may make determinations as to whatpressure to elevate the hydrocarbon feedstock and deionized water, andto operate the hydrothermal reactor 950, based on, e.g., the amount ofcontaminants in the contaminant-rich renewable hydrocarbon feedstock.

In another example, the controller 906 may determine the amount ofdeionized or other water to add via pump 945 to the effluent from thehydrothermal reactor 950 based on the amount of effluent from thehydrothermal reactor 950 and the amount of deionized water initiallyadded to the hydrocarbon feedstock at junction or flow control valve940. The controller 906 may further determine the length of time orresidence time (in other words, the time interval) that the combinedwater and feedstock may reside in the hydrothermal reactor 950 and thelength of time or residence time (in other words, the time interval)that the influent (with or without extra water) may reside in theelectrostatic precipitation unit 970. Further, the controller 906 maydetermine the temperature at which the combined water and feedstock maybe heated to while residing in the hydrothermal reactor 950 and thetemperature at which the effluent may be heated or cooled to prior toentering the electrostatic precipitation unit 970. Likewise, thecontroller 906 may determine the pressure at which the combined waterand feedstock may be elevated to (e.g., by pumps 942, 946) in thehydrothermal reactor 950. One or more pressure sensors (not shown) maybe disposed within the piping between the pumps 942, 946 and thehydrothermal reactor 950, and within the hydrothermal reactor 950itself, to ensure that the pressure has been adequately elevated. Thecontroller 906 may also determine the pressure to which the effluentshould be lowered prior to entering the electrostatic precipitation unit970, as further described below.

The controller 906 may determine the pressure drop for the effluententering the electrostatic precipitation unit 970. The effluent exitingthe hydrothermal reactor 950 may be at a pressure greater than theoperating pressure of the electrostatic precipitation unit 970. As such,the controller 906 may determine adjustments for the flow control valve964 to lower or drop the pressure of the effluent to within a range ofoperating pressures of the electrostatic precipitation unit 9704. In anexample, a pressure sensor may be disposed at the output of thehydrothermal reactor 950, at the flow control valve 964, or at somepoint in between. The pressure sensor may provide the pressure of theeffluent to the controller 906. The controller 906 may utilize such datato adjust the flow control valve 964, thus adjusting the pressure towithin the proper range of the operating pressure of the electrostaticprecipitation unit 970.

As illustrated in FIG. 10, multiple hydrothermal reactors 1050 may beutilized in parallel. In such examples, flow control valves 1054 mayenable which hydrothermal reactor 1050 may be utilized at any particulartime. For example, one hydrothermal reactor 1050 may be utilized for afirst process, while another may be utilized for a following process. Inanother example, several hydrothermal reactors 1050 may be taken offlinefor maintenance, while the rest may be utilized for further processesduring such maintenance.

As noted above, demulsifying agents may be utilized in an electrostaticprecipitation unit 1070. Such demulsifying agents may be from a chemicalsource 1061. The chemical source 1061 may be a tank storing thedemulsifying agents or another type of storage to store suchdemulsifying agents, as will be understood by those skilled in the art.

As illustrated in FIG. 11, system 1100 may include one or more oil-waterseparators (e.g., a crude desalter unit utilizing demulsifying agents, acrude desalter unit utilizing an electrostatic precipitator, anelectrostatic precipitation unit, an oil-water separator including anelectrostatic precipitator, or other type of separator). Rather thanusing the large separator as described above, a smaller first oil-waterseparator 1170A (e.g., a small Stokes Law separator, a crude desalterunit utilizing demulsifying agents, a crude desalter unit utilizing anelectrostatic precipitator, an electrostatic precipitation unit, anoil-water separator including an electrostatic precipitator, or othertype of separator) may be utilized in conjunction with and/or in serieswith the second oil-water separator 1170B (e.g., a crude desalter unitutilizing demulsifying agents, a crude desalter unit utilizing anelectrostatic precipitator, an electrostatic precipitation unit, anoil-water separator including an electrostatic precipitator, or othertype of separator). For example, as described above, a feedstock source1130, such as a storage tank, may be a renewable feedstock or otherfeedstock including contaminants (e.g., metal, phosphorus, and/or othercontaminants). Feedstock from the feedstock source 1130 may be mixedwith deionized water from a deionized water source 1124, such as aholding tank. The water used to generate the deionized water (via an ionexchange system) may be obtained from, e.g., a tank, pond, utilityprovider (via pipeline or piping), and/or other location including freshwater.

Prior to heating via heat exchanger 1148, the hydrocarbon feedstock maypass through an optional filter 1147. The filter 1147 may filter out anysolids in the hydrocarbon feedstock from the feedstock source 1130. Insuch examples, the filter 1147 may be a mesh filter, a basket filter, oranother type of filter suitable for removing solids from a liquid aswill be understood by those skilled in the art. For example, thehydrocarbon feedstock may pass through a mesh filter prior to enteringthe pump 1146 or the heat exchanger 1148. The mesh filter may be a5-micron to 50-micron mesh filter (e.g., filter 1147 may be a 10-micronmesh filter). The feedstock source 1130 and/or deionized water source1124 may be heated prior to mixing, via heat exchanger 1148 and/or heatexchanger 1144, respectively, or may be heated after mixing via, heatexchanger 1152. In another example, the mixture may be heated in thehydrothermal reactor 1150. The heated mixture may undergo a hydrothermalreaction within the hydrothermal reactor 1150, based on the temperature,pressure, flow, and/or residence time in the hydrothermal reactor 1150,to wash the inorganic contaminants from the hydrocarbon feedstock intothe deionized water.

Once the mixture has undergone the hydrothermal reaction, the mixturemay be transported to the first oil-water separator 1170A. As noted, thefirst oil-water separator 1170A may be a Stokes' law separator, a crudedesalter unit utilizing demulsifying agents, a crude desalter unitutilizing an electrostatic precipitator, an electrostatic precipitationunit, an oil-water separator including an electrostatic precipitator, orother type of separator. In an example, the separator 1170A may be atank to store the mixture for a period of time. During the period oftime, the oil or feedstock may separate and a skimmer may separate andtransport the oil to junction or flow control valve 1179. The remainingwater may be drained and/or transported via pipeline or piping 1072A fordisposal, re-use, or treatment or the remaining water may be transportedfor re-use at junction or flow control valve 1167. In such examples, thehydrocarbon feedstock, after undergoing the hydrothermal reaction, maystill include about 1.5%, 2%, about 4%, or even about 6% of water (e.g.,contaminant-rich water).

The hydrocarbon feedstock from the first oil-water separator 1170A maybe transported to junction or flow control valve 1179. At junction orflow control valve 1179, additional water (e.g., deionized water fromwater source 1124 via pump 1146, recycled water from the first oil-waterseparator 1170A, and/or second oil-water separator 1170B) and/orchemicals (e.g., demulsifying chemicals) from chemical source 1161 maybe mixed with the hydrocarbon feedstock. In such examples, the amount ofwater added may be about 1% to about 10% of the total of the mixture ofthe additional water and the feedstock (i.e., the feedstock which maystill include about 1.5%, 2%, about 4%, or even about 6% ofcontaminant-rich water after passing through the first oil-waterseparator 1170A).

During the residence time that the mixture is in the first oil-waterseparator 1170A, the mixture may cool. As such, another heat exchanger(not shown) may be disposed in the system 1100 to heat or cool thefeedstock transported from the first oil-water separator 1170A, to heator cool the additional deionized or other water, and/or to heat themixture of the additional water and the hydrocarbon feedstock from thefirst oil-water separator 1170A prior to entering the second oil-waterseparator 1170B.

Once the new mixture of feedstock and additional water have been heatedor cooled to a selected temperature (e.g., for a crude desalter unitabout 100° F. to about 300° F.), the new mixture may be transported tothe second oil-water separator 1170B (e.g., a secondary oil-waterseparator unit and/or a crude desalter unit). In the second oil-waterseparator 1170B, all or a substantial portion of the water may beremoved from the mixture. For example, all but about 0.7%, about 0.5% oreven about 0.3% of the water may be removed from the mixture. The waterremoved may include the contaminants or a portion of the contaminantsleftover from the first oil-water separator 1170A. The water may betransported from the second oil-water separator 1170B via pipeline orpiping 1172B disposal, re-use, or treatment or via junction or flowcontrol valve 1169B for re-use in the first oil-water separator 1170Aand/or second oil water separator 1170B. The pre-treated hydrocarbonfeedstock, which may be free of or substantially free of contaminants,i.e., a reduced-contaminant feedstock, may be transported via pipelineor piping 1174 to various downstream refinery equipment, such as one ormore hydroprocessing units, a fractionation column, and/or distillationtower.

FIG. 12 is a simplified diagram illustrating a control system or system1200 for managing the removal of inorganic contaminants, includingmetals, from a renewable hydrocarbon feedstock, according to anembodiment of the disclosure. As noted above, the controller 1200 mayinclude memory 1206 and a processor 1204 (or one or more processors).The memory 1206 may store instructions and the instructions may beexecutable by the processor 1204. The instructions may includeinstructions 1208 to control the various valves, flow control valves, orother components (e.g., water control valve 1218 and/or feedstockcontrol valve 1220) to control or adjust ratios and/or pressure of waterand feedstock transported to a hydrothermal cleaning unit 1232 (alsoreferred to as a HCU or hydrothermal reactor). The controller 1202 mayalso control the amount of water to mix with effluent from thehydrothermal cleaning unit. The controller 1202 may also connect to andcontrol an effluent flow control valve disposed between an HCU andelectrostatic precipitation unit. The controller 1202 may determine thepressure of the effluent and, based on the pressure of the effluent andthe operating pressure of the electrostatic precipitator, the controller1202 may lower the pressure via the effluent flow control valve.

The controller 1202 may also include instructions 1210 to control pumpsdisposed throughout the system 1200. For example, the system 1200 mayinclude a water pump 1222 to control, via signals from the controller1202, the flow of water throughout the system 1200 and/or a feedstockpump 1224 to control, via signals from the controller 1202, the flow offeedstock throughout the system 1200. In such examples, the controller1202 may determine the amount of water to mix with feedstock and/or theamount of water to mix with effluent from the hydrothermal cleaningunit, based on various factors, such as type of feedstock, estimated oractual amount of contaminants in the effluent, operating temperature,and/or operating power.

The controller 1202 may also include instructions 1212 to control heatexchangers disposed throughout the system 1200. For example, the system1200 may include a feedstock heat exchanger 1226, a water heat exchanger1228, and/or an effluent heat exchanger 1230. The controller 1202 maycontrol each of the heat exchangers based on the operating temperaturefor each process in the system 1200. For example, the hydrothermalcleaning unit 1232 may operate at temperatures between 465° F. and 575°F. Thus the controller 1202 may determine (for example, via sensors orother devices disposed throughout the system 1200) the temperature of aliquid, and based on the process to be performed and an operatingtemperature, may send a signal to a heat exchanger to heat the liquid tothe proper temperature. In other examples, the system 1200 may or maynot include an effluent heat exchanger 1230. In such examples, theeffluent may be heated or cooled to a sufficient level as the effluentis transported from the hydrothermal cleaning unit 1232.

The controller 1202 may include instructions 1214 to control thehydrothermal cleaning unit 1232 and instructions 1216 to control theelectrostatic precipitation unit 1234. For example, the controller 1202may determine the amount of time a blend of feedstock and water mayreside in the hydrothermal cleaning unit 1232 and/or in an electrostaticprecipitation unit 1234. In another example, the controller 1202 maydetermine the length of time a liquid may reside in the hydrothermalcleaning unit 1232 and/or electrostatic precipitation unit 1234.

FIG. 13 is a flow diagram, implemented in a controller, for managing theseparation of deionized water from a pre-treated hydrocarbon feedstock,according to an embodiment. The method is detailed with reference tosystem 800 of FIG. 8. Unless otherwise specified, the actions of method1300 may be completed within the controller 906 (FIG. 9). Specifically,method 1300 may be included in one or more programs, protocols, orinstructions loaded into the memory of the controller 906 and executedon the processor or one or more processors of the controller 906. Theorder in which the operations are described is not intended to beconstrued as a limitation, and any number of the described blocks may becombined in any order and/or in parallel to implement the methods.

At block 1302, the process may be initiated. In an example, a user maystart the process at a user interface connected to the controller 906.At block 1304, in response to an initiation signal, the controller 906may determine a temperature to heat the hydrocarbon feedstock to andsend a signal to heat the hydrocarbon feedstock, from a feedstock tank830 (or other source of feedstock), via a heat exchanger 848. At block1306, the controller 906 may determine a temperature to heat thedeionized water to and send a signal to heat the deionized water, from adeionized water tank 824 (or other deionized water source), via a heatexchanger 844. In another example, rather than (or in addition to)heating the hydrocarbon feedstock and/or deionized water prior tomixing, the controller 906 may send a signal to heat exchanger 852 toheat the combination or mixture of the deionized water and hydrocarbonfeedstock.

At block 1310, the hydrocarbon feedstock may be mixed with water atjunction or flow control valve 840. The controller 906 may determine theamount of deionized water to mix with the hydrocarbon feedstock based onthe type of feedstock and/or the amount of feedstock to be processed. Atblock 1312, the mixture of the deionized water and hydrocarbon feedstockmay be transported to the hydrothermal reactor 850 for washing thehydrocarbon feedstock, under elevated temperature, pressure and atnon-laminar flow, to remove inorganic contaminants. After the mixture orblend has resided in the hydrothermal reactor 850 for a sufficientamount or period of time, at block 1316, the controller 906 maydetermine (for example, via a sensor) whether the effluent is at asufficient or correct temperature and/or pressure for processing at theoil-water separation unit 870 (e.g., an electrostatic precipitationunit). If the effluent is not at the correct pressure, the flow controlvalve 864 may let down the pressure of the effluent. If the effluent isnot the correct temperature, at block 1318, the heat exchanger 862 mayheat or cool the effluent to the proper temperature. Once the effluentis at the proper temperature, at block 1320, the controller 906 maydetermine whether the amount of deionized water contained in theeffluent is sufficient. If the amount of deionized water is notsufficient, at block 1322, additional water may be added to, injectedinto the stream of, and/or incorporated with the effluent, at whichpoint the effluent may be considered influent.

Once the influent has the proper or correct amount of water and is atthe proper or correct temperature and/or pressure, the influent, atblock 1324, may be transported to the electrostatic precipitation unit870. The influent may reside in the crude desalter unit, housing theelectrostatic precipitation unit, for a specified amount of time, at aspecified temperature, and at a specified pressure. Further, a specifiedamount of power may be applied to create an electrostatic field withinthe electrostatic precipitation unit 870, thus, separating, at block1326, the contaminant-rich water from the feedstock.

This application is a continuation of U.S. Non-Provisional applicationSer. No. 17/452,678, filed Oct. 28, 2021, titled “SYSTEMS AND METHODSFOR ENHANCED INORGANIC CONTAMINANT REMOVAL FROM HYDROCARBON FEEDSTOCK,”which claims priority to and the benefit of U.S. Provisional ApplicationNo. 63/198,606, filed Oct. 29, 2020, titled “REFINERY SYSTEMS ANDMETHODS FOR SEPARATING WATER FROM PRE-TREATED FEEDSTOCK,” U.S.Provisional Application No. 63/198,937, filed Nov. 24, 2020, titled“REFINERY SYSTEMS AND METHODS FOR SEPARATING WATER AND REMOVING SOLIDSFROM PRE-TREATED AND UNFILTERED FEEDSTOCK,” and U.S. ProvisionalApplication No. 63/198,960, filed Nov. 25, 2020, titled “SYSTEMS ANDMETHODS FOR ENHANCED INORGANIC CONTAMINANT REMOVAL FROM HYDROCARBONFEEDSTOCK,” the disclosures of which are incorporated herein byreference in their entirety.

In the drawings and specification, several embodiments of systems andmethods to enhance the removal of inorganic contaminants, andparticularly metals, from a hydrocarbon feedstock have been disclosed,and although specific terms are employed, the terms are used in adescriptive sense only and not for purposes of limitation. Severalembodiments of systems and methods have been described in considerabledetail and with specific reference to the drawings. However, it will beapparent that various modifications and changes may be made within thespirit and scope of the embodiments of systems and methods as describedin the foregoing specification, and such modifications and changes areto be considered equivalents and part of this disclosure.

1. A process for reducing contaminants in renewable hydrocarbonfeedstocks at a refinery, the process comprising: passing water throughan ion exchange system to generate deionized water, the deionized waterhaving a conductivity of less than about 3 μS/cm; passing the deionizedwater through an aerator to increase a concentration of dissolved oxygenin the deionized water; mixing the deionized water with a renewablefeedstock having hydrocarbon compounds and inorganic contaminants tocreate a deionized water and renewable feedstock mixture; reacting thedeionized water and renewable feedstock mixture in a hydrothermalreactor at a temperature, pressure and non-laminar flow so as to inhibitrearrangement reactions of the renewable feedstock hydrocarboncompounds; maintaining the temperature, pressure and non-laminar flow ofthe hydrothermal reactor for a first interval of time to transfer atleast a portion of the inorganic contaminants of the renewable feedstockinto the deionized water; after the first time interval, passing thedeionized water and renewable feedstock mixture to a separation unit;separating the deionized water containing the inorganic contaminantsfrom the renewable feedstock in the separation unit to createcontaminant-rich water and a reduced-contaminant renewable feedstock fora second time interval; and after the second time interval, passing thereduced-contaminant renewable feedstock to a downstream refineryprocess.
 2. The process of claim 1, further comprising passing untreatedwater through a reverse osmosis unit to remove inorganic contaminantstherefrom to generate the water passed to the ion exchanged system. 3.The process of claim 1, wherein the deionized water constitutes greaterthan 15% by volume of the deionized water and renewable feedstockmixture, and wherein the non-laminar flow has a Reynolds number greaterthan 2,000.
 4. The process of claim 1, wherein the deionized waterconstitutes greater than 30% by volume of the deionized water andrenewable feedstock mixture.
 5. The process of claim 1, wherein thedeionized water constitutes between about 10% to about 50% by volume ofthe deionized water and renewable feedstock mixture.
 6. The process ofclaim 1, wherein the first time interval is between about 30 seconds toabout 5 minutes.
 7. The process of claim 1, wherein the temperature isbetween about 200° C. and about 450° C.
 8. The process of claim 1,wherein the renewable feedstock includes one or more of plant oils,algal and microbial oils, waste vegetable oils, yellow and brown grease,tallow, soap stock, pyrolysis oils from plastic or cellulose, andpetroleum fractions.
 9. The process of claim 1, further comprising,prior to passing the deionized water and renewable feedstock mixture tothe separation unit, injecting additional deionized water into thedeionized water and renewable feedstock mixture.
 10. The process ofclaim 9, wherein an amount of the additional deionized water is betweenabout 3% to about 10% by volume of the deionized water and renewablefeedstock mixture.
 11. The process of claim 1, wherein the second timeinterval is between 60 minutes and 180 minutes.
 12. The process of claim1, wherein the pressure is between about 500 psig and about 6,000 psig.13. The process of claim 1, wherein the deionized water in the deionizedwater and renewable feedstock mixture becomes less deionized as metalinorganic containments are transferred therein.
 14. The process of claim1, wherein the conductivity of the deionized water is less than about 1μS/cm.
 15. A process for reducing contaminants in renewable hydrocarbonfeedstocks at a refinery, the process comprising: passing water throughan ion exchange system to generate deionized water; aerating thedeionized water in an aerating unit to generate an aerated, deionizedwater; injecting the aerated, deionized water into a renewable feedstockstream at a refinery, to create a mixture of aerated, deionized waterand renewable feedstock; passing the mixture into a hydrothermal reactorat a pre-selected temperature, pressure and non-laminar flow;maintaining the temperature, pressure and non-laminar flow of thehydrothermal reactor for a first interval of time to transfer at least aportion of inorganic contaminants of the renewable feedstock into theaerated, deionized water; after the first time interval, passing themixture to a separation unit of the refinery; separating the aerated,deionized water containing the inorganic contaminants from the renewablefeedstock in the separation unit to create contaminant-rich water and areduced-contaminant renewable feedstock for a second time interval; andafter the second time interval, passing the reduced-contaminantrenewable feedstock to a downstream refinery process.
 16. The process ofclaim 15, further comprising passing untreated water through a reverseosmosis unit to remove inorganic contaminants therefrom to generate thewater passed to the ion exchange system.
 17. The process of claim 16,wherein the deionized water has a conductivity less than about 5 μS/cmthe deionized water having a conductivity less than about 5 μS/cm,wherein the deionized water constitutes between about 10% to about 50%by volume of the deionized water and renewable feedstock mixture, andwherein the non-laminar flow has a Reynolds number greater than 2,000.18. The process of claim 15, wherein the temperature is between about200° C. and about 450° C. and the pressure is between about 500 psig andabout 6,000 psig, and wherein the deionized water has a conductivityless than about 5 μS/cm the deionized water having a conductivity lessthan about 5 μS/cm.
 19. The process of claim 15, wherein the renewablefeedstock includes one or more of plant oils, algal and microbial oils,waste vegetable oils, yellow, white and brown grease, fish oil, tallow,soap stock, pyrolysis oils from plastic or cellulose, and petroleumfractions, and wherein the deionized water has a conductivity less thanabout 5 μS/cm the deionized water having a conductivity less than about5 μS/cm.
 20. The process of claim 15, further comprising, prior topassing the aerated deionized water and renewable feedstock mixture tothe separation unit, injecting additional aerated deionized water intothe aerated deionized water and renewable feedstock mixture, and whereinthe deionized water has a conductivity less than about 5 μS/cm.
 21. Theprocess of claim 20, wherein an amount of the additional deionized wateris between about 3% to about 10% by volume of the deionized water andrenewable feedstock mixture.
 22. The process of claim 15, wherein theconductivity of the deionized water is less than about 1 μS/cm.
 23. Theprocess of claim 15, further comprising adding an acid to the aerated,deionized water prior to injecting the aerated, deionized water into therenewable feedstock stream.
 24. A refinery system for reducingcontaminants in renewable hydrocarbon feedstocks, the system comprising:a source of a renewable feedstock having hydrocarbons compounds andinorganic contaminants; a source of water; a deionized water generatorin fluid communication with the source of water, the deionized watergenerator operating to generate a stream of deionized water having aconductivity less than a selected threshold; a mixer in fluidcommunication with the source of renewable feedstock and in fluidcommunication with the deionized water stream, the mixer configured toreceive the deionized water stream and renewable feedstock stream and tocreate a mixture of deionized water and renewable feedstock; an aerationunit configured to aerate at least one of the water from the watersource or the deionized water from deionized water stream prior to beingreceived by the mixer; a hydrothermal cleaning unit, positioned at arefinery, in fluid communication with the mixer to receive the mixture,the hydrothermal cleaning unit configured to transfer inorganiccontaminants contained in the renewable feedstock into the deionizedwater during a first time interval; an oil-water separator, at therefinery in fluid communication with the hydrothermal cleaning unit, theoil-water separator receiving the mixture from the hydrothermal cleaningunit and providing a residence time to separate the renewable feedstockfrom the deionized water containing the inorganic contaminants, therebygenerating a reduced-contaminant renewable feedstock; and a downstreamrefinery process unit in fluid communication with the oil-waterseparator and configured to receive the reduced-contaminant renewablefeedstock.
 25. The system of claim 24, further comprising pipingconfigured to inject additional deionized water into the mixture ofdeionized water and renewable feedstock at a location between thehydrothermal reactor and the oil-water separator.
 26. A process forreducing contaminants in renewable hydrocarbon feedstocks at a refinery,the process comprising: passing untreated water through a reverseosmosis unit to remove inorganic contaminants therefrom; passing thewater from the reverse osmosis unit through an ion exchange system togenerate deionized water, the deionized water having a conductivity lessthan a selected threshold; mixing the deionized water with a renewablefeedstock having hydrocarbon compounds and inorganic contaminants tocreate a deionized water and renewable feedstock mixture; reacting thedeionized water and renewable feedstock mixture in a hydrothermalreactor at a temperature, pressure and non-laminar flow that does notcause rearrangement reactions of the renewable feedstock hydrocarboncompounds; maintaining the temperature, pressure and non-laminar flow ofthe hydrothermal reactor for a first interval of time to transfer atleast a portion of the inorganic contaminants of the renewable feedstockinto the deionized water; after the first time interval, passing thedeionized water and renewable feedstock mixture to a separation unit;separating the deionized water containing the inorganic contaminantsfrom the renewable feedstock in the separation unit to createcontaminant-rich water and a reduced-contaminant renewable feedstock fora second time interval; and after the second time interval, passing thereduced-contaminant renewable feedstock to a downstream refineryprocess.
 27. The process of claim 26, wherein the preselected thresholdis about 5 μS/cm, and wherein the non-laminar flow has a Reynolds numbergreater than 2,000.